EP0441187A2 - Use of (meth)acryloylaminoalkylesters of carboxylic acids as adhesive components for the treatment of collagen containing materials - Google Patents
Use of (meth)acryloylaminoalkylesters of carboxylic acids as adhesive components for the treatment of collagen containing materials Download PDFInfo
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- EP0441187A2 EP0441187A2 EP91100878A EP91100878A EP0441187A2 EP 0441187 A2 EP0441187 A2 EP 0441187A2 EP 91100878 A EP91100878 A EP 91100878A EP 91100878 A EP91100878 A EP 91100878A EP 0441187 A2 EP0441187 A2 EP 0441187A2
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- meth
- methyl
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- carboxylic acid
- collagen
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- 0 CC(COC(C(C)=C)=O)OC(NC*(CC1)CC2C1C1C(C*)C2CC1)=O Chemical compound CC(COC(C(C)=C)=O)OC(NC*(CC1)CC2C1C1C(C*)C2CC1)=O 0.000 description 7
- IXKVYHYYPPQHDR-UHFFFAOYSA-N CC(CCC1)(CCCC1(C)OC(NC)=O)OC(NC)=O Chemical compound CC(CCC1)(CCCC1(C)OC(NC)=O)OC(NC)=O IXKVYHYYPPQHDR-UHFFFAOYSA-N 0.000 description 1
- OQGHPWJUTHMVMS-UHFFFAOYSA-N CC(COC(C=C)=O)OC(NC)=O Chemical compound CC(COC(C=C)=O)OC(NC)=O OQGHPWJUTHMVMS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/40—Primers
Definitions
- the invention relates to preparations for use as an adhesive component for the treatment of collagen-containing materials, processes for producing and the use of these preparations.
- the claimed preparations contain carboxylic acid (meth) acryloylaminoalkyl esters (I) of the formula in the R1 Means hydrogen or methyl, R2 Methylene or ethylene means and R3 represents hydrogen, methyl or ethyl and optionally additives such as initiators, solvents and fillers.
- Materials containing collagen are scaffold protein bodies and main components of human and animal intercellular support substances such as cartilage and bone tissue, skin and dentin.
- the adhesive components are preferably used for the treatment of dentin in connection with tooth repairs.
- Another method is to etch the dentin and the enamel surface with acids, such as phosphoric acid, and then fill it. Apart from the fact that the acid has an irritating effect in the mouth area, it also easily penetrates through the dentine channels into the tooth and damages the nerve (pulp).
- acids such as phosphoric acid
- aldehyde-containing methacrylates of the isomeric hydroxybenzaldehydes are described, which can be used as primers for fillings in the dental field.
- the bond between dentin and filling compound remains unsatisfactory even after such a primer.
- EP-A 0 141 324 describes compositions of an aldehyde and an olefinically unsaturated monomer with active hydrogen, which have a bond to dentine.
- the new preparations based on carboxylic acid (meth) acryloylamino alkyl esters (I) bring about a strong bond between materials that are to be attached to the collagen, e.g. a composite adhesion of tooth filling material in a cavity on the tooth.
- the carboxylic acid (meth) acryloylaminoalkyl esters (I) are known synthetic intermediates and were used, for example, as a monomer component for the preparation of copolymers (DE-OS 2 217 746, DE-OS 1 927 642, DE-OS 3 619 914).
- Carboxylic acid (meth) acryloylaminomethyl esters were obtained by esterification of the N-hydroxymethyl (meth) acrylamide (DE-OS 1 927 642, DE-OS 1 281 438). Carboxylic acid (meth) acryloylaminomethyl esters can be prepared accordingly from N-2-hydroxyethyl (meth) acrylamide (JA 60 262 805).
- carboxylic acid (meth) acryloylaminoalkyl esters may be mentioned as constituents of the preparations according to the invention:
- carboxylic acid (meth) acryloylaminomethyl esters of the formulas are particularly preferred:
- Initiators in the context of the present invention are radical formers which trigger free-radical polymerization.
- Photoinitiators which trigger free-radical polymerization under the action of light for example UV light, visible light or laser light, are preferred.
- photo polymerization initiators are known per se (Houben-Weyl, Methods of Organic Chemistry, Volume E 20, page 80 ff, Georg Thieme Verlag Stuttgart 1987). They are preferably mono- or dicarbonyl compounds, such as benzoin and its derivatives, in particular benzoin methyl ether, benzil and benzene derivatives, for example 4,4-oxidibenzil and other dicarbonyl compounds, such as diacetyl, 2,3-pentanedione and ⁇ -diketo derivatives of norbornane and substituted Norbornanes, metal carbonyls such as pentacarbonyl manganese or quinones such as 9,10-phenanthrenequinone and naphthoquinone. Camphorquinone is particularly preferred.
- the preparations according to the invention generally contain 0.01 to 2 parts by weight, preferably 0.1 to 0.5 parts by weight, of the initiator, based on 100 parts by weight of polymerizable compounds. If one of the joining parts in contact with the adhesive component according to the invention already contains an initiator of the type described, the initiator in the adhesive component can also be dispensed with entirely.
- the solvents in the context of the present invention should dissolve the component and, depending on the application, should be non-toxic.
- Water and volatile organic solvents such as methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, methyl or ethyl acetate and tetrahydrofuran are preferred.
- 10 to 1000% by weight, preferably 50 to 300% by weight, of the solvent, based on the carboxylic acid (meth) acryloylaminoalkyl ester, is used.
- Suitable accelerators are, for example, amines such as p-toluidine, dimethyl-p-toluidine, trialkylamines such as trihexylamine, polyamines such as N, N, N ', N'-tetraalkylalkylene diamine, barbituric acid and dialkyl barbituric acid.
- the coactivators are generally used in an amount of 0.02 to 4% by weight, preferably 0.2 to 1% by weight, based on the amount of polymerizable compounds.
- compositions according to the invention can contain carbonyl compounds as a further component.
- Carbonyl compounds in the context of the present invention are aldehydes and ketones which are 1 to 20, preferred 1 to 10, and particularly preferably 2 to 6, carbon atoms.
- the carbonyl function can be bound to an aliphatic, aromatic or heterocyclic part of the molecule.
- Aliphatic mono- or dialdehydes may be mentioned as aldehydes.
- Formaldehyde, acetaldehyde, propionaldehyde, 2-methylpropionaldehyde, butyraldehyde, benzaldehyde, vanillin, furfural, anisaldehyde, salicylaldehyde, glyoxal, glutardialdehyde and phthaldialdehyde are preferred.
- Glutardialdehyde is particularly preferred.
- Aliphatic mono- and diketones are particularly mentioned as ketones.
- Cyclopentanone is particularly preferred.
- compositions according to the invention can contain (meth) acrylic acid esters as a further component, which can form crosslinks.
- (Meth) acrylic acid esters that can form crosslinks generally contain 2 or more polymerizable active groups in the Molecule. Esters of (meth) acrylic acid with 2- to 5-valent alcohols with 2 to 30 carbon atoms are preferred. Alkoxy (meth) acrylates and (meth) acrylates containing urethane groups are particularly preferred.
- mixtures of the various (meth) acrylic acid esters that can form crosslinks For example, mixtures of 20 to 70 wt .-% bis-GMA and 30 to 80 wt .-% triethylene glycol dimethacrylate may be mentioned.
- the preparations according to the invention generally contain 5 to 80% by weight, preferably 10 to 60% by weight, of carboxyl compounds, based on the carboxylic acid (meth) acryloylaminoalkyl ester.
- compositions according to the invention can contain fillers as a further component.
- Fine powders which have a particle diameter in the range from 0.1 to 100 ⁇ m (optionally also in a polydisperse distribution).
- Fillers can be fillers customary in the dental field (RS Baratz, J. Biomat. Applications, Vol 1, 1987 , S 316 ff) such as inorganic glasses, silicon dioxide, aluminum oxide or quartz powder.
- a proportion of fillers in the preparations according to the invention results in adhesive cements which are particularly suitable for fastening bridge, crown and other veneering materials.
- the proportion of the filler is generally 20 to 80% by weight, preferably 40 to 70% by weight, based on the entire preparation.
- the adhesive components according to this invention can furthermore contain up to 10% by weight of conventional additives such as stabilizers, inhibitors, light stabilizers, dyes, pigments or fluorescent substances.
- the preparations according to the invention can be prepared by mixing the carboxylic acid (meth) acryloylaminoalkyl ester and the initiator and optionally the other components by vigorous stirring.
- the preparations can also be solvent-free.
- the preparations according to the invention can be used as an adhesive component for the treatment of materials containing collagen.
- the collagen-containing material is conditioned with a liquid having a pH in the range from 0.1 to 3.5 before treatment with the preparation according to the invention.
- the conditioning acids can contain the following acids, for example: Phosphoric acid, nitric acid, pyruvic acid, citric acid, oxalic acid, ethylenediaminetetraacetic acid, acetic acid, tartaric acid, malic acid, maleic acid.
- amphoteric amino compounds are mentioned: glycine, serine, threonine, cysteine, tyrosine, asparagine, glutamine, alanine, valine, leucine, isoleucine, proline, methionine, phenylalanine, tryptophan, lysine, arginine, histidine, N-phenylglycine, ethylene chloride Ethylene diamine hydrobromide, propylene diamine hydrochloride, propylene diamine hydrobromide, butylene diamine hydrochloride, butylene diamine hydrobromide, leucine hydrochloride and histidine hydrochloride.
- the conditioning liquid can also contain substances from the group of polyethylene glycols and metal hydroxides.
- the polybasic acids listed above can also be used as partial metal salts as long as free acid functions remain.
- Conditioning liquids which contain at least one of the acids from the group of pyruvic acid, ethylenediaminetetraacetic acid and citric acid and optionally an amphoteric amino compound from the group of glycine, N-phenylglycine and prolin are particularly preferred.
- the preparations according to the invention can be used, for example, as follows: In the case of a tooth repair, for example after mechanical cleaning of the tooth material containing collagen, the conditioning liquid is first applied with a little wetting, left to act for a short time (for example 60 seconds), the tooth material is rinsed with water and dried in an air stream. Then the preparation according to the invention is applied, for example with a small brush, in a thin layer and dried in a stream of air. After the treatment according to the invention, the actual filling compound is carried, for example plastic filling materials customary in the dental field (K. Eichner, "Dental materials and their processing", Vol. 2, p. 135 ff, Frankfurthig Verlag, 5th ed. 1985).
- the preparations according to the invention can be used for fastening crowns, bridges and similar aids.
- the adhesives according to the invention are produced by intensive mixing of the components listed in the following examples.
- the suitability of the adhesives according to Examples 1 to 3 is checked by determining the tensile bond strength of the light-activated plastic filling material based on multifunctional methacrylic acid esters and barium aluminum silicate LUMIFOR® Light Curing Composite Universal (U) on dentin.
- Extracted human teeth were used for the experiments, which were kept in a 1% chloramine solution for a maximum of 3 months after the extraction. After these teeth were carefully cleaned under running water, they were kept in physiological saline until they were embedded in epoxy resin (Lekutherm X 257).
- the tooth is sanded wet until a sufficiently large dentin surface is exposed to bind a plastic filling material cylinder of ⁇ 3.5 mm.
- the exposed dentin surface was finally prepared wet with 600 silicon carbide paper.
- the dentin is successively pretreated with the EDTA conditioning liquid GLUMA® Cleanser (60 seconds cleaning with a cotton pellet, water rinsing, air drying) and the adhesive (60 seconds exposure time, air drying).
- GLUMA® Cleanser 60 seconds cleaning with a cotton pellet, water rinsing, air drying
- adhesive 60 seconds exposure time, air drying
- the dentine sample prepared as described is clamped in a tripod with a cylindrical, divisible Teflon shape. This overall 5 mm high Teflon shape is conical in the upper half, so that a tensile test can be carried out with an appropriately shaped adapter.
- a closure material based on multifunctional methacrylic acid ester BAYER RESIN L® is applied in a thin layer with a brush to the pretreated dentin surface and additionally distributed with an air stream.
- the closure material is first irradiated at a distance of 5 mm from the dentin surface with a polymerization lamp (Translux CL, from Kulzer). This is followed by an incremental mold filling and light activation of the plastic filling material.
- a polymerization lamp Translux CL, from Kulzer
- the light activation time for the plastic filling material is set at a total of 160 seconds.
- test specimen After completion of the light activation, the test specimen is removed and stored in a water bath at 23 ° C. until the tongue test.
- the tensile bond strength, force at break of the sample divided by the contact area to the dentin, was measured at a feed rate of 1 mm / min. measured.
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- Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Dental Preparations (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
Die Erfindung betrifft Zubereitungen zur Verwendung als Adhäsivkomponente zur Behandlung kollagenhaltiger Materialien, Verfahren zur Herstellung und die Verwendung dieser Zubereitungen.The invention relates to preparations for use as an adhesive component for the treatment of collagen-containing materials, processes for producing and the use of these preparations.
Die beanspruchten Zubereitungen enthalten Carbonsäure-(meth)acryloylaminoalkylester (I) der Formel
in der
R¹
Wasserstoff oder Methyl bedeutet,
R²
Methylen oder Ethylen bedeutet
und
R³
für Wasserstoff, Methyl oder Ethyl steht und gegebenenfalls Zusätze wie Initiatoren, Lösungsmittel und Füllstoffe.The claimed preparations contain carboxylic acid (meth) acryloylaminoalkyl esters (I) of the formula
in the
R¹
Means hydrogen or methyl,
R²
Methylene or ethylene means
and
R³
represents hydrogen, methyl or ethyl and optionally additives such as initiators, solvents and fillers.
Kollagenhaltige Materialien sind Gerüsteiweißkörper und Hauptbestandteile dar menschlichen und tierischen interzellularen Stützsubstanzen wie Knorpel- und Knochengewebe, Haut und Zahnbein (Dentin). Im Rahmen der vorliegenden Erfindung werden die Adhäsivkomponenten bevorzugt zur Behandlung von Dentin im Zusammenhang mit Zahnreparaturen verwandet.Materials containing collagen are scaffold protein bodies and main components of human and animal intercellular support substances such as cartilage and bone tissue, skin and dentin. In the context of the present invention, the adhesive components are preferably used for the treatment of dentin in connection with tooth repairs.
Besonders im Dentalbereich werden härtende, polymere Materialien als Füllmaterialien bei Zahnreparaturen verwendet. Als härtende, polymere Materialien werden im allgemeinen Füllungen auf Acrylatbasis bevorzugt. Diese polymeren Füllungen haben jedoch den Nachteil, daß sie schlecht am Dentin haften bleiben. Um dieses Problem zu lösen, hat man bisher teilweise Unterschneidungen am Zahnbein vorgenommen; dazu war es erforderlich, über den angegriffenen Bereich hinaus, beachtliche Mengen an gesundem Dentin zu entfernen.In the dental sector in particular, hardening, polymeric materials are used as filling materials in tooth repairs. Fillings based on acrylate are generally preferred as hardening, polymeric materials. However, these polymeric fillings have the disadvantage that they adhere poorly to the dentin. In order to solve this problem, undercuts on the dentine have been partially made up to now; For this it was necessary to remove considerable amounts of healthy dentin beyond the affected area.
Nach einer anderen Methode ätzt man das Dentin und die Schmelzoberfläche mit Säuren, wie z.B. Phosphorsäure, an, und nimmt dann die Füllung vor. Abgesehen davon, daß die Säure eine Reizwirkung im Mundbereich ausübt, dringt sie auch leicht durch die Dentinkanäle in den Zahn und schädigt den Nerv (Pulpa).Another method is to etch the dentin and the enamel surface with acids, such as phosphoric acid, and then fill it. Apart from the fact that the acid has an irritating effect in the mouth area, it also easily penetrates through the dentine channels into the tooth and damages the nerve (pulp).
In J. Dent. Res. 57, 500-505 (1978), werden aldehydgruppenhaltige Methacrylate der isomeren Hydroxybenzaldehyde beschrieben, die als Grundierungsmittel für Füllungen im Dentalbereich verwendet werden können. Die Bindung zwischen Dentin und Füllmasse bleibt jedoch auch nach einer solchen Grundierung unbefriedigend.In J. Dent. Res. 57 , 500-505 (1978), aldehyde-containing methacrylates of the isomeric hydroxybenzaldehydes are described, which can be used as primers for fillings in the dental field. However, the bond between dentin and filling compound remains unsatisfactory even after such a primer.
In Scand. J. Dent. Res. 92, 980-983 (1984) und J. Dent. Res. 63, 1087-1089 (1984) werden Grundierungsmittel aus wäßrigem Formaldehyd oder Glutaraldehyd und β-Hydroxyethylmethacrylat (HEMA) beschrieben.In Scand. J. Dent. Res. 92 , 980-983 (1984) and J. Dent. Res. 63 , 1087-1089 (1984), primers from aqueous formaldehyde or glutaraldehyde and β-hydroxyethyl methacrylate (HEMA) are described.
Außerdem sind in der EP-A 0 141 324 Zusammensetzungen aus einem Aldehyd und einem olefinisch ungesättigten Monomer mit aktivem Wasserstoff beschrieben, die eine Anbindung an Dentin aufweisen.In addition, EP-A 0 141 324 describes compositions of an aldehyde and an olefinically unsaturated monomer with active hydrogen, which have a bond to dentine.
Die neuen Zubereitungen auf Basis von Carbonsäure-(meth)acryloylaminoalkylestern (I) bewirken eine starke Verbundhaftung von Materialien, die am Kollagen befestigt werden sollen, z.B. eine Verbundhaftung von Zahnfüllungsmaterial in einer Kavität am Zahn.The new preparations based on carboxylic acid (meth) acryloylamino alkyl esters (I) bring about a strong bond between materials that are to be attached to the collagen, e.g. a composite adhesion of tooth filling material in a cavity on the tooth.
Die Carbonsäure-(meth)acryloylaminoalkylester (I) sind bekannte Synthesezwischenstufen und wurden z.B. als Monomerbestandteil zur Herstellung von Copolymeren verwendet (DE-OS 2 217 746, DE-OS 1 927 642, DE-OS 3 619 914).The carboxylic acid (meth) acryloylaminoalkyl esters (I) are known synthetic intermediates and were used, for example, as a monomer component for the preparation of copolymers (DE-OS 2 217 746, DE-OS 1 927 642, DE-OS 3 619 914).
Carbonsäure-(meth)acryloylaminomethylester wurden durch Veresterung des N-Hydroxymethyl(meth)acrylamids erhalten (DE-OS 1 927 642, DE-OS 1 281 438). Carbonsäure-(meth)acryloylaminomethylester lassen sich entsprechend aus dem N-2-Hydroxyethyl(meth)acrylamid (JA 60 262 805) herstellen.Carboxylic acid (meth) acryloylaminomethyl esters were obtained by esterification of the N-hydroxymethyl (meth) acrylamide (DE-OS 1 927 642, DE-OS 1 281 438). Carboxylic acid (meth) acryloylaminomethyl esters can be prepared accordingly from N-2-hydroxyethyl (meth) acrylamide (JA 60 262 805).
Die gute Wirksamkeit der Carbonsäure-(meth)acryloylaminoalkylester (I) in den erfindungsgemäßen Zubereitungen als Adhäsivkomponente für kollagenhaltige Materialien war überraschend, weil sie keine reaktiven Gruppen enthalten, die unter milden Bedingungen geeignete chemische Bindungen zu kollagenhaltigen Materialien aufbauen können, was bislang als eine wichtige Voraussetzung angenommen wurde (J.C. Sectos, Am. J. Dent. 1. (1988) 173).The good effectiveness of the carboxylic acid (meth) acryloylaminoalkyl esters (I) in the preparations according to the invention as an adhesive component for collagen-containing materials was surprising because they do not contain any reactive groups which can form suitable chemical bonds to collagen-containing materials under mild conditions, which was previously important Prerequisite was accepted (JC Sectos, Am. J. Dent. 1 (1988) 173).
Beispielsweise seien die folgenden Carbonsäure-(meth)acryloylaminoalkylester als Bestandteile der erfindungsgemäßen Zubereitungen genannt:
Besonders bevorzugt sind die Carbonsäure-(meth)acryloylaminomethylester der Formeln:
Initiatoren im Rahmen der vorliegenden Erfindung sind Radikalbildner, die eine radikalische Polymerisation auslösen. Bevorzugt sind Fotoinitiatoren, die unter der Einwirkung von Licht, beispielsweise UV-Licht, sichtbarem Licht oder Laserlicht, eine radikalische Polymerisation auslösen.Initiators in the context of the present invention are radical formers which trigger free-radical polymerization. Photoinitiators which trigger free-radical polymerization under the action of light, for example UV light, visible light or laser light, are preferred.
Die sogenannten Fotopolymerisationsinitatoren sind an sich bekannt (Houben-Weyl, Methoden der organischen Chemie, Band E 20, Seite 80 ff, Georg Thieme Verlag Stuttgart 1987). Vorzugsweise handelt es sich um Mono- oder Dicarbonylverbindungen, wie Benzoin und dessen Derivate, insbesondere Benzoinmethylether, Benzil und Benzilderivate, beispielsweise 4,4-Oxidibenzil und andere Dicarbonylverbindungen wie Diacetyl, 2,3-Pentandion und α-Diketo-Derivate des Norbornans und substituierter Norbornane, Metallcarbonyle wie Pentacarbonylmangan oder Chinone wie 9,10-Phenanthrenchinon und Naphthochinon. Besonders bevorzugt ist Campherchinon.The so-called photo polymerization initiators are known per se (Houben-Weyl, Methods of Organic Chemistry, Volume E 20, page 80 ff, Georg Thieme Verlag Stuttgart 1987). They are preferably mono- or dicarbonyl compounds, such as benzoin and its derivatives, in particular benzoin methyl ether, benzil and benzene derivatives, for example 4,4-oxidibenzil and other dicarbonyl compounds, such as diacetyl, 2,3-pentanedione and α-diketo derivatives of norbornane and substituted Norbornanes, metal carbonyls such as pentacarbonyl manganese or quinones such as 9,10-phenanthrenequinone and naphthoquinone. Camphorquinone is particularly preferred.
Die erfindungsgemäßen Zubereitungen enthalten im allgemeinen 0,01 bis 2 Gew.-Teile, bevorzugt 0,1 bis 0,5 Gew.-Teile des Initiators, bezogen auf 100 Gew.-Teil an polymerisierbaren Verbindungen. Enthält eines der mit der erfindungsgemäßen Adhäsivkomponente im Kontakt stehenden Fügeteile bereits einen Initiator der beschriebenen Art, kann auf den Initiator in der Adhäsivkomponente auch ganz verzichtet werden.The preparations according to the invention generally contain 0.01 to 2 parts by weight, preferably 0.1 to 0.5 parts by weight, of the initiator, based on 100 parts by weight of polymerizable compounds. If one of the joining parts in contact with the adhesive component according to the invention already contains an initiator of the type described, the initiator in the adhesive component can also be dispensed with entirely.
Die Lösungsmittel im Rahmen der vorliegenden Erfindung sollen die Komponente lösen und sollen, durch die Anwendung bedingt, untoxisch sein. Bevorzugt seien Wasser und flüchtige organische Lösungsmittel wie Methanol, Ethanol, Propanol, Isopropanol, Aceton, Methylethylketon, Essigsäuremethyl- oder -ethylester und Tetrahydrofuran genannt.The solvents in the context of the present invention should dissolve the component and, depending on the application, should be non-toxic. Water and volatile organic solvents such as methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, methyl or ethyl acetate and tetrahydrofuran are preferred.
Im allgemeinen setzt man 10 bis 1000 Gew.-%, bevorzugt 50 bis 300 Gew.-% des Lösungsmittels, bezogen auf den Carbonsäure-(meth)acryloylaminoalkylester ein.In general, 10 to 1000% by weight, preferably 50 to 300% by weight, of the solvent, based on the carboxylic acid (meth) acryloylaminoalkyl ester, is used.
Es kann vorteilhaft sein, den erfindungsgemäßen Zubereitungen Coaktivatoren zuzusetzen, die die Polymerisationsreaktion beschleunigen. Bekannte Beschleuniger sind beispielsweise Amine wie p-Toluidin, Dimethyl-p-toluidin, Trialkylamine wie Trihexylamin, Polyamine wie N,N,N',N'-Tetraalkylalkylendiamin, Barbitursäure und Dialkylbarbitursäure.It can be advantageous to add coactivators to the preparations according to the invention which accelerate the polymerization reaction. Known accelerators are, for example, amines such as p-toluidine, dimethyl-p-toluidine, trialkylamines such as trihexylamine, polyamines such as N, N, N ', N'-tetraalkylalkylene diamine, barbituric acid and dialkyl barbituric acid.
Die Coaktivatoren werden im allgemeinen in einer Menge von 0,02 bis 4 Gew.-%, bevorzugt 0,2 bis 1 Gew.-%, bezogen auf die Menge an polymerisierbaren Verbindungen eingesetzt.The coactivators are generally used in an amount of 0.02 to 4% by weight, preferably 0.2 to 1% by weight, based on the amount of polymerizable compounds.
Als weitere Komponente können die erfindungsgemäßen Zusammensetzungen Carbonylverbindungen enthalten.The compositions according to the invention can contain carbonyl compounds as a further component.
Carbonylverbindungen im Rahmen der vorliegenden Erfindung sind Aldehyde und Ketone, die 1 bis 20, bevorzugt 1 bis 10, und besonders bevorzugt 2 bis 6 Kohlenstoffatome, enthalten. Die Carbonylfunktion kann an einem aliphatischen, aromatischen oder heterocyclischen Molekülteil gebunden sein.Carbonyl compounds in the context of the present invention are aldehydes and ketones which are 1 to 20, preferred 1 to 10, and particularly preferably 2 to 6, carbon atoms. The carbonyl function can be bound to an aliphatic, aromatic or heterocyclic part of the molecule.
Als Aldehyde seien aliphatische Mono- oder Dialdehyde genannt. Bevorzugt wird Formaldehyd, Acetaldehyd, Propionaldehyd, 2-Methylpropionaldehyd, Butyraldehyd, Benzaldehyd, Vanillin, Furfural, Anisaldehyd, Salicylaldehyd, Glyoxal, Glutardialdehyd und Phthaldialdehyd. Besonders bevorzugt ist der Glutardialdehyd.Aliphatic mono- or dialdehydes may be mentioned as aldehydes. Formaldehyde, acetaldehyde, propionaldehyde, 2-methylpropionaldehyde, butyraldehyde, benzaldehyde, vanillin, furfural, anisaldehyde, salicylaldehyde, glyoxal, glutardialdehyde and phthaldialdehyde are preferred. Glutardialdehyde is particularly preferred.
Als Ketone seien besonders aliphatische Mono- und Diketone genannt. Bevorzugt sind Butanon, Aceton, Cyclooctanon, Cycloheptanon, Cyclohexanon, Cyclopentanon, Acetophenon, Benzophenon, 1-Phenyl-2-propanon, 1,3-Diphenyl-2-propanon, Acetylaceton, 1,2-Cyclohexandion, 1,2-Cyclopentandion und Campherchinon. Besonders bevorzugt ist Cyclopentanon.Aliphatic mono- and diketones are particularly mentioned as ketones. Butanone, acetone, cyclooctanone, cycloheptanone, cyclohexanone, cyclopentanone, acetophenone, benzophenone, 1-phenyl-2-propanone, 1,3-diphenyl-2-propanone, acetylacetone, 1,2-cyclohexanedione, 1,2-cyclopentanedione and Camphorquinone. Cyclopentanone is particularly preferred.
Im allgemeinen setzt man 1 bis 1000 Gew.-%, bevorzugt 5 bis 50 Gew.-% der Carbonylverbindungen, bezogen auf den Carbonsäure-(meth)acryloylaminoalkylester ein.In general, 1 to 1000% by weight, preferably 5 to 50% by weight, of the carbonyl compounds, based on the carboxylic acid (meth) acryloylaminoalkyl ester, are used.
Als weitere Komponente können die erfindungsgemäßen Zusammensetzungen (Meth)-acrylsäureester enthalten, die Vernetzungen ausbilden können. (Meth)-acrylsäureester, die Vernetzungen ausbilden können, enthalten im allgemeinen 2 oder mehr polymerisierbare aktive Gruppen im Molekül. Bevorzugt seien Ester der (Meth)-acrylsäure mit 2- bis 5-wertigen Alkoholen mit 2 bis 30 Kohlenstoffatomen genannt. Besonders bevorzugt werden Alkoxy(meth)acrylate und Urethangruppen enthaltende (Meth)acrylate.The compositions according to the invention can contain (meth) acrylic acid esters as a further component, which can form crosslinks. (Meth) acrylic acid esters that can form crosslinks generally contain 2 or more polymerizable active groups in the Molecule. Esters of (meth) acrylic acid with 2- to 5-valent alcohols with 2 to 30 carbon atoms are preferred. Alkoxy (meth) acrylates and (meth) acrylates containing urethane groups are particularly preferred.
Beispielsweise seien (Meth)acrylsäureester der Formel
in der
- A
- einen geradkettigen, verzweigten, cyclischen, aliphatischen, aromatischen oder gemischt aliphatischaromatischen Rest mit 2 bis 25 C-Atomen, der durch -O-, NH- oder O-CO-NH-Brücken unterbrochen und mit Hydroxy, Oxy, Carboxy, Amino oder Halogen substituiert sein kann,
bedeutet, - R
- H oder Methyl bedeutet und
- n
- für eine ganze Zahl von 2 bis 8, vorzugsweise 2 bis 4, steht,
genannt.
in the
- A
- a straight-chain, branched, cyclic, aliphatic, aromatic or mixed aliphatic-aromatic radical with 2 to 25 carbon atoms, which is interrupted by -O-, NH- or O-CO-NH bridges and with hydroxy, oxy, carboxy, amino or halogen can be substituted
means - R
- Is H or methyl and
- n
- represents an integer from 2 to 8, preferably 2 to 4,
called.
Vorzugsweise seien Verbindungen der folgenden Formeln genannt:
in der ortho-, meta- oder para-Form
- n
- eine Zahl von 1 bis 4 und
- m
- eine Zahl von 0 bis 5 bedeutet.
in the ortho, meta or para form
- n
- a number from 1 to 4 and
- m
- means a number from 0 to 5.
Außerdem seien Derivate des Tricyclodecans (EP-A-00 23 686) und Umsetzungsprodukte aus Polyolen, Diisocyanaten und Hydroxyalkylmethacrylaten (DE-A-37 03 120, DE-A-37 03 080 und DE-A-37 03 130) genannt. Beispielsweise seien die folgenden Monomeren genannt:
Besonders bevorzugt als Monomer wird das sogenannte Bis-GMA der Formel
Selbstverständlich ist es möglich, Mischungen der verschiedenen (Meth)-Acrylsäureester, die Vernetzungen ausbilden können, einzusetzen. Beispielsweise seien Mischungen von 20 bis 70 Gew.-% Bis-GMA und 30 bis 80 Gew.-% Triethylenglykoldimethacrylat genannt.Of course, it is possible to use mixtures of the various (meth) acrylic acid esters that can form crosslinks. For example, mixtures of 20 to 70 wt .-% bis-GMA and 30 to 80 wt .-% triethylene glycol dimethacrylate may be mentioned.
Die erfindungsgemäßen Zubereitungen enthalten im allgemeinen 5 bis 80 Gew.-%, bevorzugt 10 bis 60 Gew.-% Carboxylverbindungen, bezogen auf den Carbonsäure-(meth)acryloylaminoalkylester.The preparations according to the invention generally contain 5 to 80% by weight, preferably 10 to 60% by weight, of carboxyl compounds, based on the carboxylic acid (meth) acryloylaminoalkyl ester.
Als weitere Komponente können die erfindungsgemäßen Zusammensetzungen Füllstoffe enthalten. Als Füllstoffe werden feine Pulver bevorzugt, die einen Teilchendurchmesser im Bereich von 0,1 bis 100 µm (gegebenenfalls auch in einer polydispersen Verteilung) haben. Füllstoffe können im Dentalbereich übliche Füllstoffe (R. S. Baratz, J. Biomat. Applications, Vol 1, 1987, S 316 ff) wie anorganische Gläser, Siliziumdioxid-, Aluminiumoxid- oder Quarzpulver sein.The compositions according to the invention can contain fillers as a further component. Fine powders which have a particle diameter in the range from 0.1 to 100 μm (optionally also in a polydisperse distribution). Fillers can be fillers customary in the dental field (RS Baratz, J. Biomat. Applications, Vol 1, 1987 , S 316 ff) such as inorganic glasses, silicon dioxide, aluminum oxide or quartz powder.
Durch einen Anteil an Füllstoffen in den erfindungsgemäßen Zubereitungen entstehen Klebezemente, die besonders zur Befestigung von Brücken-, Kronen- und anderen Verblendmaterialen geeignet sind.A proportion of fillers in the preparations according to the invention results in adhesive cements which are particularly suitable for fastening bridge, crown and other veneering materials.
Der Anteil des Füllstoffs beträgt im allgemeinen 20 bis 80 Gew.-%, bevorzugt 40 bis 70 Gew.-%, bezogen auf die gesamte Zubereitung.The proportion of the filler is generally 20 to 80% by weight, preferably 40 to 70% by weight, based on the entire preparation.
Die Adhäsivkomponenten gemäß dieser Erfindung können weiterhin bis zu 10 Gew.-% üblicher Zusätze wie Stabilisatoren, Inhibitoren, Lichtschutzmittel, Farbstoffe, Pigmente oder Fluoreszenzstoffe enthalten.The adhesive components according to this invention can furthermore contain up to 10% by weight of conventional additives such as stabilizers, inhibitors, light stabilizers, dyes, pigments or fluorescent substances.
Die erfindungsgemäßen Zubereitungen können hergestellt werden, indem man den Carbonsäure-(meth)acryloylaminoalkylester und den Initiator und gegebenenfalls die anderen Komponenten durch kräftiges Rühren mischt.The preparations according to the invention can be prepared by mixing the carboxylic acid (meth) acryloylaminoalkyl ester and the initiator and optionally the other components by vigorous stirring.
Die Zubereitungen können auch lösungsmittelfrei vorliegen.The preparations can also be solvent-free.
Die erfindungsgemäßen Zubereitungen können als Adhäsivkomponente zur Behandlung kollagenhaltiger Materialien verwendet werden.The preparations according to the invention can be used as an adhesive component for the treatment of materials containing collagen.
In einer besonderen Ausführungsform konditioniert man das kollagenhaltige Material vor der Behandlung mit der erfindungsgemäßen Zubereitung mit einer Flüssigkeit mit einem pH-Wert im Bereich von 0,1 bis 3,5.In a particular embodiment, the collagen-containing material is conditioned with a liquid having a pH in the range from 0.1 to 3.5 before treatment with the preparation according to the invention.
Diese enthalt im allgemeinen Säuren mit einem pKs-Wert kleiner als 5 und gegebenenfalls eine amphotere Aminoverbindung mit einem pKs-Wert im Bereich von 9,0 bis 10,6 und einem pKB-Wert im Bereich von 11,5 bis 12,5. Folgende Säuren können z.B. in der Konditionierflüssigkeit enthalten sein:
Phosphorsäure, Salpetersäure, Brenztraubensäure, Zitronensäure, Oxalsäure, Ethylendiamintetraessigsäure, Essigsäure, Weinsäure, Äpfelsäure, Maleinsäure.This contains, in general, acids with a pK less than 5, and optionally an amphoteric amino compound having a pK value in the range from 9.0 to 10.6 and a pK B value in the range of 11.5 to 12, 5. The conditioning acids can contain the following acids, for example:
Phosphoric acid, nitric acid, pyruvic acid, citric acid, oxalic acid, ethylenediaminetetraacetic acid, acetic acid, tartaric acid, malic acid, maleic acid.
Als amphotere Aminoverbindungen seien vorzugsweise Verbindungen der Formel
in der
R⁵
für eine Carboxylgruppe steht,
R⁶
Wasserstoff, gegebenenfalls durch Hydroxy, Thio, Methylthio, Carboxy, Amino, Phenyl, Hydroxy-phenyl oder die Gruppen
R⁷
Wasserstoff oder Phenyl bedeutet,
wobei die Reste R⁵ und R⁷ durch einen Propylrest verbunden sein können, oder
in der
R⁵
für Wasserstoff steht,
R⁶
für die Gruppe
-B-NH₃X,
in der
- B
- für einen zweibindigen Alkylenrest mit 1 bis 6 Kohlenstoffatomen und
- X
- für Halogen steht,
bedeutet und
R⁷
Wasserstoff bedeutet,
genannt.Preferred amphoteric amino compounds are compounds of the formula
in the
R⁵
represents a carboxyl group,
R⁶
Hydrogen, optionally by hydroxy, thio, methylthio, carboxy, amino, phenyl, hydroxyphenyl or the groups
R⁷
Means hydrogen or phenyl,
wherein the radicals R⁵ and R⁷ can be connected by a propyl radical, or
in the
R⁵
represents hydrogen,
R⁶
for the group
-B-NH₃X,
in the
- B
- for a divalent alkylene radical with 1 to 6 carbon atoms and
- X
- represents halogen,
means and
R⁷
Hydrogen means
called.
Beispielsweise seien die folgenden amphoteren Aminoverbindungen genannt: Glycin, Serin, Threonin, Cystein, Tyrosin, Asparagin, Glutamin, Alanin, Valin, Leucin, Isoleucin, Prolin, Methionin, Phenylalanin, Tryptophan, Lysin, Arginin, Histidin, N-Phenylglycin, Ethylendiaminhydrochlorid, Ethylendiaminhydrobromid, Propylendiaminhydrochlorid, Propylendiaminhydrobromid, Butylendiaminhydrochlorid, Butylendiaminhydrobromid, Leucinhydrochlorid und Histidinhydrochlorid.For example, the following amphoteric amino compounds are mentioned: glycine, serine, threonine, cysteine, tyrosine, asparagine, glutamine, alanine, valine, leucine, isoleucine, proline, methionine, phenylalanine, tryptophan, lysine, arginine, histidine, N-phenylglycine, ethylene chloride Ethylene diamine hydrobromide, propylene diamine hydrochloride, propylene diamine hydrobromide, butylene diamine hydrochloride, butylene diamine hydrobromide, leucine hydrochloride and histidine hydrochloride.
Weiterhin kann die Konditionierflüssigkeit Stoffe aus der Gruppe der Polyethylenglykole und Metallhydroxide enthalten. Insbesondere können die oben aufgeführten mehrbasigen Säuren auch als teilweise Metallsalze eingesetzt werden solange freie Säurefunktionen verbleiben.The conditioning liquid can also contain substances from the group of polyethylene glycols and metal hydroxides. In particular, the polybasic acids listed above can also be used as partial metal salts as long as free acid functions remain.
Konditionierflüssigkeiten, die mindestens eine der Säuren aus der Gruppe der Brenztraubensäure, Ethylendiamintetraessigsäure und Zitronensäure sowie gegebenenfalls eine amphotere Aminoverbindung aus der Gruppe des Glycins, N-Phenylglycins und Prolins enthalten, sind besonders bevorzugt.Conditioning liquids which contain at least one of the acids from the group of pyruvic acid, ethylenediaminetetraacetic acid and citric acid and optionally an amphoteric amino compound from the group of glycine, N-phenylglycine and prolin are particularly preferred.
Die Anwendung der erfindungsgemäßen Zubereitungen kann beispielsweise wie folgt durchgeführt werden:
Bei einer Zahnreparatur trägt man beispielsweise nach einer mechanischen Reinigung des kollagenhaltigen Zahnmaterials zuerst die Konditionierflüssigkeit mit etwas Wette auf, läßt eine kurze Zeit (beispielsweise 60 Sekunden) einwirken, spült das Zahnmaterial mit Wasser und trocknet es im Luftstrom. Dann trägt man die erfindungsgemäße Zubereitung beispielsweise mit einem kleinen Pinsel in einer dünnen Schicht auf und trocknet im Luftstrom. Nach der erfindungsgemäßen Behandlung trägt man die eigentliche Füllmasse, beispielsweise im Dentalbereich übliche Kunststoffüllungsmassen (K. Eichner, "Zahnärztliche Werkstoffe und ihre Verarbeitung", Bd. 2, S. 135 ff, Hüthig Verlag, 5. Aufl. 1985) auf.The preparations according to the invention can be used, for example, as follows:
In the case of a tooth repair, for example after mechanical cleaning of the tooth material containing collagen, the conditioning liquid is first applied with a little wetting, left to act for a short time (for example 60 seconds), the tooth material is rinsed with water and dried in an air stream. Then the preparation according to the invention is applied, for example with a small brush, in a thin layer and dried in a stream of air. After the treatment according to the invention, the actual filling compound is carried, for example plastic filling materials customary in the dental field (K. Eichner, "Dental materials and their processing", Vol. 2, p. 135 ff, Hüthig Verlag, 5th ed. 1985).
In ähnlicher Weise können die erfindungsgemäßen Zubereitungen zur Befestigung von Kronen, Brücken und ähnlichen Hilfsmitteln verwendet werden.In a similar way, the preparations according to the invention can be used for fastening crowns, bridges and similar aids.
Die erfindungsgemäßen Klebemittel werden durch intensives Vermischen der in folgenden Beispielen aufgeführten Bestandteile erzeugt.The adhesives according to the invention are produced by intensive mixing of the components listed in the following examples.
46 g Essigsäuremethacryloylaminomethylester der Formel
54 g Wasser
125 mg Campherchinon46 g of methyl acetic acid aminomethyl ester of the formula
54 g water
125 mg camphorquinone
40 g Essigsäuremethacryloylaminomethylester
42 g Wasser
18 g 25 gew.-%ige wäßrige Glutardialdehyd-Lösung
125 mg Campherchinon40 g of methyl acetate
42 g water
18 g 25% by weight aqueous glutardialdehyde solution
125 mg camphorquinone
35 g Propionsäuremethacryloylaminomethylester der Formel
20 g 25 gew.-%ige wäßrige Glutardialdehyd-Lösung
10 g Tetrahydrofuran
125 mg Campherchinon35 g of methacryloylaminomethyl propionate of the formula
20 g 25% by weight aqueous glutardialdehyde solution
10 g tetrahydrofuran
125 mg camphorquinone
Die Eignung der Klebemittel entsprechend der Beispiele 1 bis 3 wird geprüft, indem die Zugbindungsfestigkeit des lichtaktivierten Kunststoffüllungsmaterials auf Basis mehrfunktioneller Methacrylsäureester und Bariumaluminiumsilikat LUMIFOR® Light Curing Composite Universal (U), auf Dentin bestimmt wird.The suitability of the adhesives according to Examples 1 to 3 is checked by determining the tensile bond strength of the light-activated plastic filling material based on multifunctional methacrylic acid esters and barium aluminum silicate LUMIFOR® Light Curing Composite Universal (U) on dentin.
Für die Versuche werden extrahierte menschlische Zähne verwendet, die maximal 3 Monate nach der Extraktion in 1 % Chloraminlösung aufbewahrt wurden. Nachdem diese Zähne sorgfältig unter fließend Wasser gereinigt wurden, erfolgte die Aufbewahrung bis zur Einbettung in Expoxidharz (Lekutherm X 257) in physiologischer Kochsalzlösung.Extracted human teeth were used for the experiments, which were kept in a 1% chloramine solution for a maximum of 3 months after the extraction. After these teeth were carefully cleaned under running water, they were kept in physiological saline until they were embedded in epoxy resin (Lekutherm X 257).
Unter Verwendung von Schleifpapier unterschiedlicher Körnung wird der Zahn naß angeschliffen bis eine hinreichend große Dentinfläche zur Abbindung eines Kunststoffüllungsmaterialcylinders von ⌀ 3,5 mm freiliegt. Die freigelegte Dentinfläche wurde naß mit Siliziumcarbidpapier 600 abschließend präpariert.Using abrasive paper of different grain sizes, the tooth is sanded wet until a sufficiently large dentin surface is exposed to bind a plastic filling material cylinder of ⌀ 3.5 mm. The exposed dentin surface was finally prepared wet with 600 silicon carbide paper.
Das Dentin wird nacheinander mit der EDTA-Konditionierflüssigkeit GLUMA® Cleanser (60 Sekunden Reinigung mit einem Wattepellet, Wasserspülung, Lufttrocknung) und dem Klebemittel (60 Sekunden Einwirkzeit, Lufttrocknung) vorbehandelt.The dentin is successively pretreated with the EDTA conditioning liquid GLUMA® Cleanser (60 seconds cleaning with a cotton pellet, water rinsing, air drying) and the adhesive (60 seconds exposure time, air drying).
Zur Herstellung des Probekörpers für den Zugbindungsversuch, wird die wie beschrieben präparierte Dentinprobe in ein Stativ mit einer zylindrischen, teilbaren Teflonform gespannt. Diese insgesamt 5 mm hohe Teflonform ist in der oberen Hälfte konisch ausgeführt, so daß mit einem entsprechend geformten Adapter ein Zugversuch durchgeführt werden kann.To produce the test specimen for the tensile bond test, the dentine sample prepared as described is clamped in a tripod with a cylindrical, divisible Teflon shape. This overall 5 mm high Teflon shape is conical in the upper half, so that a tensile test can be carried out with an appropriately shaped adapter.
Ein Verschlußmaterial auf Basis mehrfunktioneller Methacrylsäureester BAYER RESIN L® wird in dünner Schicht mit einem Pinsel auf die vorbehandelte Dentinoberfläche aufgetragen und mit einem Luftstrom zusätzlich verteilt.A closure material based on multifunctional methacrylic acid ester BAYER RESIN L® is applied in a thin layer with a brush to the pretreated dentin surface and additionally distributed with an air stream.
Das Verschlußmaterial wird zunächst im Abstand von 5 mm zur Dentinoberfläche mit einer Polymerisationsleuchte (Translux CL, Fa Kulzer) bestrahlt. Danach erfolgt ein incrementales Formfüllen und Lichtaktivieren des Kunststoffüllungsmaterials.The closure material is first irradiated at a distance of 5 mm from the dentin surface with a polymerization lamp (Translux CL, from Kulzer). This is followed by an incremental mold filling and light activation of the plastic filling material.
Die Lichtaktivierungszeit für das Kunststoffüllungsmaterial wird aufgrund des großen Volumens mit insgesamt 160 Sekunden angesetzt.Due to the large volume, the light activation time for the plastic filling material is set at a total of 160 seconds.
Nach Abschluß der Lichtaktivierung wird der Probekörper entfernt und bis zum Zungversuch im Wasserbad bei 23°C gelagert.After completion of the light activation, the test specimen is removed and stored in a water bath at 23 ° C. until the tongue test.
Die Zugbindungsfestigkeit, Kraft beim Bruch der Probe dividiert durch das Kontaktareal zum Dentin, wurde mit einer Vorschubgeschwindigkeit von 1 mm/min. gemessen.The tensile bond strength, force at break of the sample divided by the contact area to the dentin, was measured at a feed rate of 1 mm / min. measured.
Die Bruchfläche am Dentin wird anschließend lichtmikroskopisch zur Beurteilung der Versagensursache überprüft. Hierbei waren vielfach Kohäsivfrakturen zu beobachten, d.h. die mit den erfindungsgemäßen Adhäsivkomponenten erzeugten Verklebungen waren fester als die verklebten Fügeteile selbst. Dies zeigt die gute Leistungsfähigkeit der erfindungsgemäßen Adhäsivkomponenten.The fracture surface on the dentin is then checked by light microscopy to assess the cause of the failure. Cohesive fractures were often observed here, ie the bonds produced with the adhesive components according to the invention were stronger than the bonded parts themselves. This shows the good performance of the adhesive components according to the invention.
Claims (13)
R¹
Wasserstoff oder Methyl bedeutet,
R²
Methylen oder Ethylen bedeutet
und
R³
für Wasserstoff, Methyl oder Ethyl steht und gegebenenfalls Zusätze wie Initiatoren, Lösungsmittel und Füllstoffe als Adhäsivkomponente zur Behandlung kollagenhaltiger Materialien.Preparation containing carboxylic acid (meth) acryloylamino alkyl ester (I) of the formula
R¹
Means hydrogen or methyl,
R²
Methylene or ethylene means
and
R³
represents hydrogen, methyl or ethyl and optionally additives such as initiators, solvents and fillers as an adhesive component for the treatment of collagen-containing materials.
worin
R¹
Wasserstoff oder Methyl bedeutet,
R²
Methylen bedeutet,
R³
für Wasserstoff oder Methyl steht.Preparation according to Claim 1, containing carboxylic acid (meth) acryloylaminoalkyl ester,
wherein
R¹
Means hydrogen or methyl,
R²
Methylene means
R³
represents hydrogen or methyl.
R¹
Wasserstoff oder Methyl bedeutet,
R²
Methylen oder Ethylen bedeutet
und
R³
für Wasserstoff, Methyl oder Ethyl steht und gegebenenfalls Zusätze wie Initiatoren und Füllstoffe in einem Lösungsmittel mischt.Process for the preparation of preparations for use as an adhesive component for the treatment of materials containing collagen, characterized in that carboxylic acid (meth) acryloylaminoalkyl esters of the formula
R¹
Means hydrogen or methyl,
R²
Methylene or ethylene means
and
R³
represents hydrogen, methyl or ethyl and optionally mixes additives such as initiators and fillers in a solvent.
R¹
Wasserstoff oder Methyl bedeutet,
R²
Methylen oder Ethylen bedeutet
und
R³
für Wasserstoff, Methyl oder Ethyl steht und gegebenenfalls Zusätze wie Initiatoren, Lösungsmittel und Füllstoffe als Adhäsivkomponente zur Behandlung kollagenhaltiger Materialien.Use of preparations containing carboxylic acid (meth) acryloylaminoalkyl esters of the formula
R¹
Means hydrogen or methyl,
R²
Methylene or ethylene means
and
R³
represents hydrogen, methyl or ethyl and optionally additives such as initiators, solvents and fillers as an adhesive component for the treatment of collagen-containing materials.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4003435A DE4003435A1 (en) | 1990-02-06 | 1990-02-06 | CARBONIC ACID (METH) ACRYLOYLAMINOALKYL ESTERS IN ADHAESIVE COMPONENTS FOR THE TREATMENT OF COLLAGEN-CONTAINING MATERIALS |
| DE4003435 | 1990-02-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0441187A2 true EP0441187A2 (en) | 1991-08-14 |
| EP0441187A3 EP0441187A3 (en) | 1992-05-13 |
Family
ID=6399498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19910100878 Withdrawn EP0441187A3 (en) | 1990-02-06 | 1991-01-24 | Use of (meth)acryloylaminoalkylesters of carboxylic acids as adhesive components for the treatment of collagen containing materials |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5207577A (en) |
| EP (1) | EP0441187A3 (en) |
| JP (1) | JPH04211003A (en) |
| DE (1) | DE4003435A1 (en) |
| IE (1) | IE910381A1 (en) |
| PT (1) | PT96661A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5558516A (en) * | 1994-10-14 | 1996-09-24 | Minnesota Mining And Manufacturing Company | Pretreated plastic dental appliances and methods |
| US5730601A (en) * | 1996-03-11 | 1998-03-24 | The Regents Of The University Of Colorado | Method and material for use with dental composites for improving conversion of monomers to polymers and reducing volume shrinkage |
| DE19643007A1 (en) * | 1996-10-18 | 1998-04-23 | Martin Dr Schaerfe | Bonding agent for improving the adhesion between tooth substance and fillings, bonding agents for artificial teeth, etc |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0051796A1 (en) * | 1980-11-06 | 1982-05-19 | Henkel Kommanditgesellschaft auf Aktien | Storage-stable, aerobically curable polymer compositions, especially reactive adhesives, containing boron compounds |
| EP0141324A2 (en) * | 1983-10-25 | 1985-05-15 | Bayer Ag | Adhesion promoting agent, process for its preparation and use thereof on collageneous material |
| DE3619914A1 (en) * | 1985-06-13 | 1986-12-18 | Canon K.K., Tokio/Tokyo | THROUGH BLASTING WITH EFFECTIVE ENERGY RESINABLE RESIN MIXTURE |
| EP0394792A1 (en) * | 1989-04-27 | 1990-10-31 | Bayer Ag | (Meth)acrylic acid derivatives containing formyl piperazine groups |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1123475B (en) * | 1960-09-13 | 1962-02-08 | Roehm & Haas Gmbh | Process for the production of polymerisation plastics |
| BE627745A (en) * | 1962-01-31 | |||
| DE3510611A1 (en) * | 1985-03-23 | 1986-09-25 | Bayer Ag, 5090 Leverkusen | COATING MATERIAL FOR COLLAGEN-CONTAINING MATERIALS |
| US4910268A (en) * | 1987-04-22 | 1990-03-20 | Shiro Kobayashi | Acryl type macromonomer having a polyethyleneimine derivative chain and process for producing the same, as well as graft polymer having a polyethyleneimine derivative chain as the graft chain and process for producing the same |
-
1990
- 1990-02-06 DE DE4003435A patent/DE4003435A1/en not_active Withdrawn
-
1991
- 1991-01-24 EP EP19910100878 patent/EP0441187A3/en not_active Withdrawn
- 1991-01-25 US US07/646,562 patent/US5207577A/en not_active Expired - Fee Related
- 1991-01-31 JP JP3029166A patent/JPH04211003A/en active Pending
- 1991-02-04 PT PT96661A patent/PT96661A/en unknown
- 1991-02-05 IE IE038191A patent/IE910381A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0051796A1 (en) * | 1980-11-06 | 1982-05-19 | Henkel Kommanditgesellschaft auf Aktien | Storage-stable, aerobically curable polymer compositions, especially reactive adhesives, containing boron compounds |
| EP0141324A2 (en) * | 1983-10-25 | 1985-05-15 | Bayer Ag | Adhesion promoting agent, process for its preparation and use thereof on collageneous material |
| DE3619914A1 (en) * | 1985-06-13 | 1986-12-18 | Canon K.K., Tokio/Tokyo | THROUGH BLASTING WITH EFFECTIVE ENERGY RESINABLE RESIN MIXTURE |
| EP0394792A1 (en) * | 1989-04-27 | 1990-10-31 | Bayer Ag | (Meth)acrylic acid derivatives containing formyl piperazine groups |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4003435A1 (en) | 1991-08-08 |
| JPH04211003A (en) | 1992-08-03 |
| PT96661A (en) | 1991-10-31 |
| US5207577A (en) | 1993-05-04 |
| IE910381A1 (en) | 1991-08-14 |
| EP0441187A3 (en) | 1992-05-13 |
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